WO2002059168A1 - Procedes de production de polymere d'addition de cycloolefine - Google Patents

Procedes de production de polymere d'addition de cycloolefine Download PDF

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Publication number
WO2002059168A1
WO2002059168A1 PCT/JP2002/000453 JP0200453W WO02059168A1 WO 2002059168 A1 WO2002059168 A1 WO 2002059168A1 JP 0200453 W JP0200453 W JP 0200453W WO 02059168 A1 WO02059168 A1 WO 02059168A1
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Prior art keywords
group
cyclic olefin
addition polymer
compound
cyclic
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PCT/JP2002/000453
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English (en)
Japanese (ja)
Inventor
Kenzo Ohkita
Noboru Oshima
Takashi Imamura
Takashi Tsubouchi
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Jsr Corporation
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Priority to US10/466,429 priority Critical patent/US6911507B2/en
Priority claimed from JP2001015318A external-priority patent/JP4894986B2/ja
Priority claimed from JP2001227249A external-priority patent/JP4941621B2/ja
Priority claimed from JP2001227248A external-priority patent/JP5013033B2/ja
Application filed by Jsr Corporation filed Critical Jsr Corporation
Priority to DE60226310T priority patent/DE60226310T2/de
Priority to EP02710329A priority patent/EP1364975B1/fr
Publication of WO2002059168A1 publication Critical patent/WO2002059168A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/903—Monomer polymerized in presence of transition metal containing catalyst and hydrocarbon additive affecting polymer properties of catalyst activity

Definitions

  • the present invention relates to a method for producing a cyclic olefin-based addition polymer. More specifically, the addition of a monomer component containing at least one kind of cyclic olefin containing a polar group in a hydrocarbon solvent using a specific polymerization catalyst without the need for a large amount of alkylaluminoxane. And a method for producing a cyclic olefin-based addition polymer. Further, the present invention relates to a method for producing a cyclic olefin-based addition polymer having an aromatic vinyl group at a polymer terminal.
  • the present invention relates to a method for producing a cyclic olefin-based addition polymer having a controlled molecular weight and molecular weight distribution. Further, the present invention relates to a method for further improving polymerization activity in the production of a cyclic olefin-based addition polymer.
  • a cyclic olefin polymer As a plastic material having the above-mentioned high transparency and thermal stability, a cyclic olefin polymer has been proposed.
  • a hydride of a ring-opened polymer Japanese Patent No. 3501196, Japanese Unexamined Patent Application Publication No. No. 1 3 2 6 2 5, JP JP-A-11-32626, etc.
  • addition copolymers of cyclic olefins and ethylene JP-A-61-292601, Makromol. Chem. Macromol. Symp. Vol.
  • hydrides of ring-opened polymers were not always satisfactory in terms of heat resistance because it was difficult to achieve a glass transition temperature of 200 ° C. or higher.
  • traces of double bonds that are not hydrogenated often remain in the molecular chains, which may cause problems such as coloring at high temperatures.
  • addition polymers of cyclic olefins which are polymerized using late transition metal compounds such as nickel and palladium as catalysts, can be manufactured with glass transition temperatures exceeding 200 ° C and have extremely high heat resistance It can also be suitably used for applications where properties are required. In addition, it is possible to control the glass transition temperature and add functions by selecting the monomer component.
  • Japanese Patent Application Laid-Open No. 416,807 / 1990 discloses a method for producing a norportene-based polymer using a catalyst containing a transition metal compound component and an aluminoxane component as main components.
  • the substituents of the norponene monomer include not only hydrocarbon groups but also those containing oxygen or nitrogen atoms.
  • such a monomer is not used in the Examples, and thus there is no description that a polymer containing a cyclic olefin having a polar group as a structural unit can be obtained by the method of the publication. It is clear from the examples described that the method of this publication requires a large amount of an aluminoxane component.
  • Japanese Patent Application Laid-Open No. 1989-1989 proposes an addition copolymer of norpolene and substituted norpolene, but the substituent is limited to a hydrocarbon group and has a polar group. There is no description of a polymer containing a substituted norportene as a structural unit.
  • the above-mentioned palladium catalyst system often requires a multi-step synthesis route or a combination of expensive chemicals such as a silver compound, and the cost associated with the catalyst becomes extremely high. Furthermore, since the solubility of the catalyst component in hydrocarbon solvents is low and the polymerization activity is low, halogenated hydrocarbons such as dichloromethane and chlorobenzene, nitromethane and tetramethyl Urea and the like are used as solvents. However, these solvents are not practically industrial because they are expensive and may be harmful to humans and the environment.
  • Another problem in the addition polymerization of cyclic olefins is that chain transfer is unlikely to occur, and thus controlling the molecular weight of the addition polymer becomes a problem.
  • the molecular weight of the cyclic olefin-based addition polymer is high, the solution viscosity is so high that handling becomes extremely difficult, the polymer becomes insoluble in a practical solvent, and a gel-like component is produced as a by-product, so that molding is difficult. Or impair the smoothness of the surface of the molded product.
  • an addition polymer having a low molecular weight a formed film or the like becomes brittle, and further, solvent resistance and liquid crystal resistance are reduced.
  • Methods for controlling the molecular weight of the addition polymer include controlling the amount of a polymerization catalyst and adding a molecular weight regulator.
  • the method by adjusting the amount of catalyst requires a large amount of catalyst depending on the target molecular weight, resulting in a high cost, and a metal component remaining to the extent required for optical or electronic material applications. It is not practical because it requires a great deal of cost to reduce it.
  • control of the polymerization temperature becomes difficult due to a large amount of the polymerization catalyst.
  • Japanese Patent Publication No. 11-550877 discloses copolymerization of a norpolene-type monomer and a cation-polymerizable monomer by a catalyst containing a VIII group transition metal.
  • the aromatic biel compound is excluded from both the cationically polymerizable monomer and the chain transfer agent.
  • Japanese Patent Application Laid-Open No. H11-111109 discloses a method for producing a copolymer of a norpoleneene-based monomer and a styrene-based monomer using a catalyst formed from hydrocarbon-soluble vanadium and organoaluminum. Is disclosed. Further, Japanese Patent Application Laid-Open No. 4-45113 discloses a method for producing a copolymer using a catalyst mainly composed of a nickel compound component and an aluminoxane component.
  • the styrene monomer is one of the units constituting the polymer, and is introduced into the molecular chain of the polymer.
  • hydrogen is suggested as a method for controlling the molecular weight
  • aromatic vinyl compounds for controlling the molecular weight is suggested. Neither is described nor suggested.
  • a substituent containing not only a hydrocarbon group but also an oxygen atom or a nitrogen atom is specified as a substituent of the norpoleneene-based monomer.
  • such a monomer is not used, and thus there is no description that a copolymer containing a norponene structural unit having a polar group can be obtained by the method disclosed in the publication.
  • the substituents specified on the styrene-based monomer in the publication are limited to hydrocarbon groups and halogen atoms, and a method for introducing an aromatic substituent having a polar group into a polymer is disclosed. Is not listed.
  • Japanese Patent Application Laid-Open No. 2001-197723 discloses a method for producing a copolymer of cyclic olefin and styrene into which an ion dissociating group has been introduced.
  • the method of this publication includes a step of preparing a copolymer of cyclic olefin and styrene in advance, and a step of introducing an ion-dissociating group such as a sulfonic acid group into the copolymer.
  • the polar groups that can be introduced are limited to only a small part.
  • styrene is treated as a monomer, and the molecular weight cannot be controlled by using the polymerization catalyst used in Examples, and aromatic substituents are added to the molecular chain. Nor can it be introduced selectively at the ends.
  • the present invention has been made in view of the above-described problems, and includes a cyclic olefin having a polar group in a hydrocarbon solvent using an easily accessible catalyst component and without using a large amount of aluminoxane.
  • An object of the present invention is to provide a method for producing a cyclic olefin-based addition polymer in which a monomer component is addition-polymerized.
  • Another object of the present invention is to provide a cyclic olefin-based addition polymer having an aromatic substituent at a terminal.
  • Still another object is to provide a cyclic olefin-based addition polymer having a controlled molecular weight and molecular weight distribution.
  • Another object of the present invention is to provide a method for further improving the polymerization activity in the production of a cyclic olefin addition polymer.
  • a specific polar group is prepared by using (i) a specific transition metal compound belonging to Groups 8 to 10 of the periodic table, (ii) a Lewis acid compound, and (ii) a polymerization catalyst component containing an alkylaluminoxane.
  • the present invention further provides a method for producing a cyclic olefin-based addition polymer, characterized by subjecting a cyclic olefin containing a substituted norpolene having the following to addition polymerization in a hydrocarbon solvent.
  • Cyclic olefins are prepared in a hydrocarbon solvent using (i) a specific group 8-10 transition metal compound of the periodic table, (ii) a Lewis acid compound, and (iii) a polymerization catalyst component containing an alkylaluminoxane.
  • a specific group 8-10 transition metal compound of the periodic table e.g., a Lewis acid compound
  • a polymerization catalyst component containing an alkylaluminoxane e.g., a polymerization catalyst component containing an alkylaluminoxane.
  • Polymerization using the catalyst component according to the present invention provides a substituted nor having a polar group.
  • Cyclic olefins containing polene can be subjected to addition polymerization in a hydrocarbon solvent.
  • a polar group such as an ester group or an alkoxysilyl group is used. It was found that if even a small amount of substituted norportene was present in the polymerization system, no polymerization activity was exhibited or the polymerization activity was significantly reduced.
  • the alkylaluminoxane needs to be added in an amount exceeding 100 times the amount of the nickel atom in terms of the aluminum atom.
  • the addition of an aromatic vinyl compound to the polymerization system during the addition polymerization of cyclic olefins in a hydrocarbon solvent using the catalyst component according to the present invention has the effect of increasing the gel-permeability. It has been clarified that the molecular weight of the addition polymer measured by means of the chromatography can be arbitrarily controlled, and that an aromatic substituent can be introduced into the terminal of the molecular chain.
  • the mechanism is not described in detail, but it is thought to be due to the introduction of the aromatic vinyl compound and the subsequent J3-hydrogen elimination. According to this mechanism, an aromatic substituent is introduced at the terminal of the molecular chain, and an orthogonal double bond is generated.
  • the fact that the aromatic substituent is bonded to the addition polymer is about 700 cm- 1 in the infrared absorption spectrum. Weak absorption Is confirmed by observing. Interestingly, in the nuclear magnetic resonance spectrum (NMR) of the addition polymer, the absorption attributed to the aromatic vinyl compound was observed at an intensity corresponding to the assumption that only one was introduced per molecule of the addition polymer. Was only done. That is, the aromatic vinyl compound introduced into the molecular chain does not exist or is negligible, and it is appropriate to think that the aromatic vinyl compound was selectively introduced into the molecular chain terminal.
  • NMR nuclear magnetic resonance spectrum
  • an aromatic vinyl compound having a polar group such as an alkoxysilyl group can also be used as a molecular weight regulator.
  • a catalyst containing a nickel compound component and an aluminoxane component as main components which is exemplified in the above-mentioned example of JP-A-4-145113, is a result of a study by the present inventors.
  • the polymer showed almost no polymerization ability or markedly reduced polymerization activity with respect to a polar aromatic vinyl compound such as 5,5-alkoxysilylstyrene.
  • addition polymerization proceeds while maintaining practical activity.
  • the present inventors have also found that, in addition polymerization of cyclic olefins using the catalyst component according to the present invention, cyclic non-conjugated polyene is added to the polymerization system, so that the cyclic olefin-based addition weight having a narrower molecular weight distribution is obtained. It has been clarified that the union can be obtained with an arbitrary molecular weight, and that the polymerization activity can be improved.
  • a ligand for thermally stabilizing a transition metal compound has been known, and many, for example, a transition metal dichlorooctane compound and the like have been isolated.
  • a specific ratio of a cyclic non-conjugated polyene compound and conducting polymerization a cyclic olefin-based addition polymer having a narrow molecular weight distribution can be obtained, the molecular weight can be adjusted, and the polymerization activity is further improved. There have been no reports showing that this can be obtained.
  • Hei 9-5108649 it is described that alicyclic diolefins can be added to a specific catalyst system as an electron donor of an optional third component of the catalyst. Although it is described, there is no description related to the object of the present invention, and its effect is not clear.
  • the polymerization catalyst has the following formula
  • a transition metal compound represented by the following formula can be used.
  • M is a transition metal of Groups 8 to 10 of the periodic table
  • L is a neutral ligand or a solvent molecule, such as benzene, toluene, xylene, mesitylene, etc.
  • Ether compounds such as aromatic hydrocarbons, cyclic polyenes such as 1,5-cyclooctadiene, norpolnadiene, getyl ether, dibutyl ether, and tetrahydrofuran
  • X is i3-diketonate anion or a dicarboxylic acid anion having a linear or branched alkyl group having 1 to 12 carbon atoms.
  • An is a non-coordinating or weakly-coordinating anion, and one selected from S bF 6 —, PF 6 —, BF 4 —, CF 3 S ⁇ 3 —, and CF 3 COO is preferably used.
  • the transition metal compound of the formula (1) may be synthesized using a known method as appropriate, may be used in an isolated form, or may be used without prior isolation.
  • the (i) transition metal compound represented by the formula (1) is a jS-diketonate compound of a transition metal of Groups 8 to 10 of the periodic table, or a carbon of a transition metal of Groups 8 to 10 of the periodic table.
  • the presence of the neutral ligand or the coordinating solvent represented by L can enhance the uniformity of the reaction and the stability of the product.
  • Compounds in which all the anions are replaced by strong Brönsted acid anions, which are by-produced when an excess of strong Brönsted acid compounds are added, are usually insoluble in hydrocarbon solvents, and can be removed by filtration or other methods. it can.
  • Examples of the / 3-diketonate compounds of transition metals of Groups 8 to 10 of the periodic table include nickel bisacetyl acetate, nickel nickel acetate, cobalt bisacetyl acetate, and palladium bis.
  • Examples of the carboxylate include nickel acetate, nickel propionate, nickel 2-ethylhexanoate (nickel octylate), 3,5,5 — Nickel trimethylhexanoate (nickel isononanoate), nickel octanoate, nickel naphthenate, nickel neodecanoate, nickel cyclohexylcarboxylate, nickel laurate, nickel stearate, and particularly preferably nickel bis Acetyl acetonate, nickel 2-ethylhexanoate, 3, 5, 5-tri Ji Nickel hexanoate, nickel octanoate, nickel naphthenate, nickel neodecanoate, nickel cyclohexylcarboxylate,
  • the strong Bronsted acid compound used in the present invention is preferably selected from hexafluoroantimonic acid, hexafluorophosphoric acid, tetrafluoroboric acid, trifluoromethanesulfonic acid, and trifluoroacetic acid. .
  • Lewis acid As the compound, desirably, boron trifluoride, aluminum trifluoride, titanium tetrachloride, antimony pentafluoride, tris (pentafluorophenyl) hydrogen, tris (3,5-bistrifluoromethylphenyl)
  • a material selected from boron is used, and particularly preferably, boron trifluoride, aluminum trifluoride, titanium tetrachloride, and antimony pentafluoride are used. These can be used alone or in combination of two or more kinds.
  • alkylaluminoxane used in combination with the (i) transition metal compound is represented by the following formula:
  • R 14 is an alkyl group having 1 to 20 carbon atoms, preferably a methyl group, an ethyl group, or an isobutyl group, particularly preferably a methyl group, and s is an integer of 2 or more, preferably 5 to 5. It is an integer in the range of 60.
  • Modified methylaluminoxane (hereinafter referred to as “MMA ⁇ J”), which has improved solubility and storage stability of methylaluminoxane by adding trialkylaluminum or the like, can also be used. It can be produced by a known method comprising reacting an alkyl aluminum compound having at least one R 14 group with water, and contacting the alkyl aluminum compound with a trace amount of water in a reaction vessel during polymerization. , Can also be generated.
  • the alkylaluminoxane is (i) a transition metal atom constituting the transition metal compound, which is converted into an aluminum atom, preferably from 1 It is used in a ratio of 100 times, most preferably in the range of 1 to 50 times. At that time, by decreasing the ratio, the molecular weight distribution of the obtained addition polymer can be widened, and by increasing the ratio, an addition polymer having a narrower distribution can be obtained. Use beyond the above range may be meaningless or decrease the activity of addition polymerization.
  • examples of the aromatic vinyl compound that can be used as a molecular weight regulator include styrene and substituted styrene, -methylstyrenes, 1-vinylnaphthalene, and the like. Desirably, styrene and substituted styrene are used. Specific examples of the substituted styrene include 2-methylstyrene, 2-ethylstyrene, 2-isopropylstyrene, 2-t-butylstyrene, 2-hexylstyrene, and 2,3-dimethylstyrene.
  • the aromatic substituent and the olefinic double bond introduced into the terminal of the molecular chain by the method of the present invention may further introduce or convert another functional group by a known method.
  • alkylation, halogenation, sulfonation, acylation, hydrogenation of aromatic substituents, epoxidation of olefinic double bonds, hydrosilylation, hydroboration, hydroformylation, diolation, maleic anhydride Can be added or grafted.
  • the amount of the aromatic vinyl compound added is a molar ratio with respect to the total amount of the cyclic olefin. And more than 0.01%, preferably in the range of 0.1% to 10%. If the amount is less than 0.01%, the effect of the addition of the aromatic vinyl compound becomes extremely small.
  • the cyclic non-conjugated polyene that can be used as a molecular weight regulator is desirably represented by the following formula (5).
  • R 6 to R 13 are the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogenated hydrocarbon group, an organic silicon group, a halogenated cage group. And m and n are integers of 1 to 3. ⁇
  • Unsubstituted or substituted cyclohexadienes unsubstituted or substituted cycloheptagens such as 1,4-cycloheptadiene, 1,4-cyclooctadiene, 1,5-cyclooctadiene, 1-methyl-1 1
  • unsubstituted or substituted cyclooctanes such as 1,5-dimethyl-1,5-cyclohexane, and the like, and more preferably unsubstituted or substituted cyclooctane.
  • the amount of the cyclic non-conjugated polyene used is (i) a molar ratio in the range of 0.01 to 500 times per transition metal atom constituting the transition metal compound, and preferably 0.1 to: L 0 p times. And more preferably in the range of 0.2 to 50 times. If it is less than 0.01, the effect of the cyclic non-conjugated polyene cannot be obtained, while if it is more than 500, practical catalytic activity cannot be obtained.
  • the aromatic vinyl compound and the cyclic non-conjugated polyene may be used simultaneously as a molecular weight regulator, or only one of them may be used.
  • the cyclic olefin addition polymer obtained by the method of the present invention comprises a structural unit derived from a cyclic olefin.
  • the cyclic olefin include norbornene and substituted norpolene, and specific examples thereof include a substituted norbornene having a polar group represented by the following formula (2).
  • At least one of A 1 , A 2 , A 3 , and A 4 is a polar group represented by one (CR 1 ! ⁇ 2 ) q Z, and the other is the same or different, and is hydrogen. And a group selected from an atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an aralkyl group, a cycloalkyl group and an aryl group.
  • Z is one C (O) R 3 , — OC (0) R 4 , one C (0) OR 5 or - represents S i Y 1 Y 2 Y 3 , R i R 5 are the same or different, a hydrogen atom, a hydrocarbon group or eight halogenated hydrocarbon group of from 1 to 1 0 carbon atoms and Table, ⁇ 1 ? 3 is the same or different, and at least one is a halogen atom, an alkoxy group, an aryloxy group, or a siloxy group, and the other represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogenated hydrocarbon group.
  • a 1 and A 2 or A 1 and A 3 may be closed to form a lactone or an acid anhydride.
  • P and q represent an integer of 0 to 3. ]
  • substituted norbornene having a polar substituent represented by the above formula (2) ′ include 5-trimethoxysilyl-12-norpolene, 5-chlorodimethoxysilyl1-2-norpolene, 5-dichloromethoxysilyl-12- Norpolpenene, 5-chloromethoxymethylsilyl-1-norbornene, 5-methoxymethylhydrosilyl1-2-norpolene, 5-dimethoxyhydrosilyl-2-norpolene, 5-methoxydimethylsilyl-2-norpollenene, 5-triethoxysilyl mono 2-norpolpolene, 5-chlorochloroethoxysilyl-1-norpollene, 5-dichloroethoxysilyl-2-norpollene, 5-chloroethoxysilyl-2-nornorpolene, 5-methoxyethoxysilyl-2-norpollene, 5-ethoxyl Dimethylsilyl mono
  • a substituted norportene having a polar substituent a substituted norpolene having a silyl group, such as represented by the following formula (3), is preferably used.
  • ⁇ to ⁇ 3 are the same or different, at least one is a halogen atom, an alkoxy group, an aryloxy group, or a siloxy group, and the other is a hydrogen atom, a carbon atom having 1 to 10 carbon atoms.
  • substituted norportene having a polar substituent represented by the above formula (3) include 5-trimethoxysilyl-12-norpolene, 5-chlorodimethoxysilyl-12-norpolene, 5-dichloromethoxysilyl-12-no Lupolene, 5-chloromethoxymethylsilyl-2-norpolene, 5-methoxymethylhydrosilyl_2-norpolene, 5-dimethoxyhydrosilyl-2-norbornene, 5-methoxydimethylsilyl 1-2-norpol Nene, 5-triethoxysilyl-2-norpolene, 5-chloroethoxysilyl-l-norpollene, 5-dichloro-mouth ethoxysilyl-l-nor-norpolene, 5-chloroethoxymethylsilyl-l-nornorpolene, 5-jetoxyhydrosilyl -2-norbornene, 5-ethoxyd
  • These can be used alone or as a mixture of two or more.
  • These polar group-containing substituted norpolene are preferably in a molar ratio within a range of preferably 30%, more preferably in a range of 0.1 to 30%, and most preferably in a range of 0.1 to 30%, based on the total cyclic olefin. Used in the range of 20%.
  • Specific examples of the cyclic olefins in the present invention further include non-polar cyclic olefins represented by the following formula (4). It is preferable to copolymerize in addition to the above-mentioned polar group-containing substituted norpolene.
  • B 1 , B 2 , B 3 , and B 4 are the same or different and are a hydrogen atom, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, Alkyl group, a cycloalkyl group, Ariru group, B 1 and whether the Arukiri den group formed by B 2, B 1 and B 3 and alkylene groups bonded to a cycloalkylene group, Shikuroaruke two alkylene group, an alkenylene group, Ariren And r represents an integer of 0 to 3. ]
  • 2-norpolene 5-methyl-2-norbornene, 5-ethyl-2-norpolene, 5-propyl-12-norpolene, 5-isopropylpyr-2-norporene, 5-butyl-2-norporene, 5 — T—Butyl-2-norporene, .5-pentyl-2-norpolene, 5-hexyl-2-norbornene, 5-year-octyl-2-norpolene, 5-decyl-2-norporene, 5-dodecyl-2-norporene, 5,5-Dimethyl-2-norpolene, 5,6-Dimethyl-2-norpolene, 5-methyl-5-ethyl-2-norbornene, 5-cyclohexyl-2-norpolene, tricyclo [4.3.0.I 2 '5] -3-decene, tetracyclo [4.
  • 2-norbornene tricyclo [4. 3 0 I 2.. '5] -3- decene, tetracyclo [4 4. 0 I 2.. ' 5 1 7 ⁇ .] -3 - selected from dodecene, substituted
  • These non-polar cyclic olefins are preferably present in a molar ratio of 70 to 100%, more preferably 70 to 99.9%, most preferably 80 to 99%, based on the total cyclic olefin. Used in the range of%.
  • a structural unit of an alkyl-substituted norpolene having 3 to 10 carbon atoms it is possible to improve the moldability such as controlling the solubility of the obtained polymer in a solvent and the glass transition temperature, and to obtain the obtained molding. It can give the body flexibility.
  • a structural unit of a cyclic olefin having a functional group such as an alkenyl group, an alkylidene group, an ester group, or an alkoxysilyl group
  • a crosslinking point for giving a cyclic olefin-based addition polymer a three-dimensional network structure or other materials It can also provide functions such as adhesion to the polymer and good dispersibility.
  • those containing a norbornene structural unit having an appropriate ratio of an alkoxysilyl group can be suitably used for a composite with a metal oxide such as silica, alumina and titania.
  • the cyclic olefinic addition polymer obtained by the method of the present invention may further optionally contain, as a structural unit, one or more monocyclic olefins of norpolnadiene.
  • a hydrocarbon solvent can be suitably used.
  • cycloaliphatic hydrocarbon solvents such as cyclohexane, cyclopentane, and methylcyclopentane
  • aliphatic hydrocarbons such as pentane, hexane, heptane, and octane
  • a solvent selected from a hydrogen solvent, an aromatic hydrocarbon solvent such as toluene, benzene, and xylene is used. These can be used alone or in combination of two or more.
  • the weight ratio of the solvent monomer is in the range of 1 to 20.
  • a solvent and a monomer composed of cyclic olefin, the above-mentioned molecular weight modifier, and the above-mentioned polymerization catalyst are added to a reaction vessel under a nitrogen or argon atmosphere, and the reaction is carried out at a temperature of 120 ⁇ to 100 0.
  • the polymerization is carried out in the range described above.
  • the cyclic olefin-based addition polymer of the present invention has a weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography using 0-dichlorobenzene of 10-100,000-1. , 500, 000, preferably 50, 0000 to 1, 0000, 0000.
  • weight average molecular weight is less than 10,000, the breaking strength when formed into a film, a thin film, a sheet, or the like is insufficient, and the solvent resistance and the liquid crystal resistance are poor.
  • the weight-average molecular weight exceeds 1,500,000, the processability of the sheet and film decreases, and the solution viscosity increases during casting of the cast film, making handling difficult. Become.
  • the molecular weight of the cyclic olefin-based addition polymer is adjusted by adjusting the addition amount of the aromatic vinyl compound of the present invention and Z or the cyclic non-conjugated polyene, and further, other molecular weights such as olefin and hydrogen. Simultaneous use of a regulator, adjustment of the amount of the polymerization catalyst, control of the polymerization temperature, and adjustment of the conversion to the polymer may be carried out.
  • the method of adding the aromatic vinyl compound and / or cyclic non-conjugated polyene to the polymerization system is not particularly limited, but may be added in advance to the polymerization system, or may be added together with a solvent, a monomer, or a polymerization catalyst. It may be added. Preliminary contact with the polymerization catalyst is not excluded. As described in No. 49, this is different from the method in which a cyclic non-conjugated gen is previously mixed with a transition metal compound component and a co-catalyst component as a component of a polymerization catalyst to synthesize a catalytically active species. Things.
  • the polymerization catalyst components may be independently introduced into a reaction vessel in which addition polymerization is performed, or two or more components may be mixed in advance.
  • Termination of the polymerization is carried out by a compound selected from water, alcohol, organic acid, carbon dioxide and the like.
  • the polymerization catalyst residue may be separated and removed from the addition polymerization reaction mixture, and a known method may be appropriately used. For example, a method of adding an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid or the like, or an organic acid such as maleic acid or fumaric acid to the addition polymerization reaction mixture, and washing the mixture with a water or alcohol solution may be used.
  • the cyclic olefin addition polymer can be obtained, for example, by putting an addition polymerization reaction mixture in an alcohol such as methanol, ethanol, or isopropanol, coagulating, and drying under reduced pressure. This step also removes any remaining unreacted monomers.
  • the cyclic olefin addition polymer produced by the method of the present invention is used as a composite with a metal oxide such as silica, alumina, or titania, a method of mixing in a solid state using a kneader, Mixing a solution of a metal-based addition polymer with a solvent dispersion of a metal oxide and removing the solvent, or a solution of a cyclic olefin-based addition polymer with a tetraalkoxide and / or alkyltrialkoxide such as silicon, aluminum, titanium, and zirconium Methods such as the "sol-gel method" in which hydrolysis and polycondensation are performed before or after mixing a metal trialkoxide selected from the group consisting of quinide and aryl trialkoxide, or a solution thereof.
  • a metal oxide such as silica, alumina, or titania
  • the ratio of the metal oxide in the composite is 5 to 70% by weight, and the particle size of the metal oxide cannot be uniquely determined. However, the metal oxide in the cyclic olefin-based addition polymer is not determined. Particle size of 1 When it is less than 00 nm, a transparent complex is formed. As the proportion of metal oxide having a particle size of 100 nm or more in the cyclic olefin addition polymer increases, the transparency of the composite decreases.
  • the cyclic olefin-based addition polymer produced by the method of the present invention includes a crosslinking agent containing a peroxide, a disulfide, a disulfide, a polysulfide compound, a dioxime compound, a tetrasulfide, a silane coupling agent and the like.
  • the cyclic olefin-based addition polymer may be added in an amount of 0.05 to 5 parts by weight based on 100 parts by weight, and may be converted into a crosslinked body by heat or the like, or may be directly crosslinked by light or electron beam. Can also be converted to
  • the cyclic olefin-based addition polymer produced by the method of the present invention can be formed into a molded product by a method such as injection molding, professional molding, press molding, or extrusion molding.
  • a cyclic olefin-based addition polymer is dissolved in a solvent selected from polar solvents such as solvents, ketones, ethers, esters, amines, amides, and urea, and then cast and evaporated to form thin films, films and sheets. be able to. Further, after the cyclic olefin-based addition polymer is swollen with these solvents, it can be formed into a film or a sheet while evaporating the solvent with an extruder.
  • the cyclic olefin-added polymer produced by the method of the present invention may also be used in combination with other thermoplastic resins, for example, a ring-opened (co) polymer and / or a hydride of the (co) polymer, Addition copolymer of ethylene and Z or ⁇ -olefin, polymethyl methacrylate, polyarylate, polyethylene tersulfone, polyarylene sulfide, polyethylene, polypropylene, polyester, polyamide, petroleum resin, etc. It can also be used as a finished thermoplastic polymer composition.
  • other thermoplastic resins for example, a ring-opened (co) polymer and / or a hydride of the (co) polymer, Addition copolymer of ethylene and Z or ⁇ -olefin, polymethyl methacrylate, polyarylate, polyethylene tersulfone, polyarylene sulfide, polyethylene, polypropylene, polyester, polyamide, petroleum resin, etc. It can also
  • the cyclic olefin-based addition polymer produced by the method of the present invention includes 2,6-di-t-butyl-4-methylphenol, 4,4′-thiobis (6 — T-butyl-1-3-methylphenol), 1,1'-bis (4-hydroxyphenyl) cyclohexane, 2, 2'-methylenebis (4-ethyl-6-t-butylphenol), 2,5-zy t- Butyl hydroquinone, pen erythrityl tetrakis [3- (3,5-di!;-Butyl-4-hydroxyphenyl) propionate and other phenolic and hydroquinone-based antioxidants, and tris (4-methoxy-13,5-diphenyl) Oxidation stability can be improved by adding phosphorus-based antioxidants such as phosphite and tris (nonylphenyl) phosphite.
  • phosphorus-based antioxidants such as phosphite and tris (non
  • the monomer composition ratio (mol%) in the cyclic olefin-based addition polymer was determined by appropriately using —NMR, 13 C—NMR method, and FT-IR method. .
  • Polystyrene-equivalent weight average molecular weight (Mw) and polystyrene-equivalent number average molecular weight (Mn) are as follows: o-Dichroic benzene, manufactured by Waters, USA; It was measured by chromatography.
  • the nickel atom and the antimony atom were in a ratio of 1: 2, so that 2-ethylethylanionate, which is the anion of the nickel atom, was completely desorbed and replaced with S b F 6 _. It was found that this was the compound.
  • a dry toluene solution of 2-norpolene (concentration: 5.0 mol / l) was placed in a 1 liter stainless-steel reaction vessel that had been sufficiently dried and purged with nitrogen, and then 170 ml (0.85 mol) of 5-nitroethoxy was added. 38.5 grams (0.15 mole) of silyl-2-norpolene and 400 milliliters of dry toluene were charged, and 9 millimoles of styrene dissolved in 10 milliliters of toluene were added. Was adjusted to 20 ° C.
  • Example 2 The same operation as in Example 1 was carried out except that the amount of the methylaluminoxane solution to be added was 3.2 ml and the amount of styrene was 7 mmol, to obtain 107 g (90%) of a cyclic olefin-based addition polymer. .
  • the weight average molecular weight (Mw) was 308,000, the number average molecular weight (Mn) was 120,000, and MwZMn was 2.6.
  • the molecular weight distribution was narrower than that in Example 1.
  • the content of structural units derived from norportene was 85 mol%
  • the content of structural units derived from 5-triethoxysilyl-2-norpolene was 15 mol%.
  • Example 2 The same operation as in Example 1 was performed except that the amount of the methylaluminoxane solution to be added was 6.4 ml and the amount of styrene was 5 mmol, to obtain 104 g (88%) of a cyclic olefin-based addition polymer. .
  • Weight average molecular weight (Mw) is 234,000
  • number average molecular weight (Mn) is 109,000
  • M wZMn was 2.1
  • the molecular weight distribution was narrower than in Examples 1 and 2.
  • the content of structural units derived from norbornene was 85 mol%
  • the content of structural units derived from 5-triethoxysilyl-2-norpolene was 15 mol%.
  • Example 2 The same operation as in Example 1 was carried out except that 2.5 mmol of aluminum atom was added to Modified Methylaluminoxane (manufactured by Tosoh Azozo Co., Ltd., hereinafter referred to as “MMA ⁇ -1”) instead of methylaluminoxane. Thus, 97 dara (82%) of an addition polymer was obtained.
  • the weight average molecular weight (Mw) was 341,000
  • the number average molecular weight (Mn) was 124,000
  • MwZMn was 2.8.
  • the content of structural units derived from norportene was 86 mol%
  • the content of structural units derived from 5-triethoxysilyl-2-norpolene was 14 mol%.
  • a toluene solution of both methylaluminoxane and triethylaluminum is mixed so as to have a ratio of 75/25 in terms of aluminum atoms, and then mixed with 5O.
  • the mixture was stirred for 2 hours to denature.
  • This modified aluminoxane hereinafter referred to as “MMA0-2J”
  • MMA0-2J this modified aluminoxane
  • the weight-average molecular weight (Mw) was 249,000, the number-average molecular weight (Mn) was 105,000, and MwZMn was 2.4.
  • - Analysis by NMR revealed norbornane
  • the content of the structural unit derived from styrene was 85 mol%, and the content of the structural unit derived from 5-triethoxysilyl 2-norpolonene was 15 mol%.
  • catalyst component C nickel 2-ethylhexanoate
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • MwZMn MwZMn
  • Dodeka 3 E emission (hereinafter referred to as "cyclic Orefin (I)")
  • a dry toluene solution (concentration: 3.0 mol Z liter) was charged to 1.0 milliliter and a dry toluene solution to 50 milliliter, and a dry toluene solution of 1,5-cyclooxengen (concentration: 0.1 mol / liter) was added.
  • a dry toluene solution of 1,5-cyclooxengen (concentration: 0.1 mol / liter) was added.
  • was added to the mixture and the temperature of the system was adjusted to 30 ° C while stirring.
  • Example 6 7.0 g (71%) in the same manner as in Example 6 except that the catalyst component B prepared in Reference Example 2 was used instead of the catalyst component A, and 0.025 mmol in terms of nickel atom was used.
  • Weight average molecular weight (Mw) 766, 000, Mw / Mn was 2.5.
  • the content of structural units derived from cyclic olefins (I) in the copolymer was determined to be 1.6 mol% by i fi-NMR and FT-IR analyses.
  • Example 6 The same operations as in Example 6 were performed using the catalyst components shown in Table 2. As a result, in Comparative Example 4 in which the boron trifluoride getyl ether complex was not used, no polymerization proceeded at all. In addition, when nickel 2-ethylhexanoate (catalyst component C) is used instead of catalyst component A, even if methylaluminoxane is used 10 times in terms of aluminum atoms with respect to nickel atoms. No polymer was obtained, and polymerization proceeded only with 100 times the amount, but showed only low polymerization activity. In Comparative Example 7, in which nickel bisacetylacetonate (catalyst component D) was used as the catalyst component and the boron trifluoride getyl ether complex was not used, polymerization did not proceed at all.
  • Example 8 The same operations as in Example 8 were performed using the catalyst components shown in Table 2. As a result, in Comparative Example 8 in which the catalyst component A was used and the boron trifluoride getyl ether complex was not used, although a small amount of an addition polymer was obtained, a carbonyl group was found in the FT-IR spectrum. No absorption based on the stretching vibration was observed. Comparative examples 9 and 9 using nickel 2-ethylhexanoate (catalyst component C) as the catalyst component and a boron trifluoride getyl ether complex. In the case of 1 and 10, the polymerization proceeded with low activity by using methylaluminoxane 100 times as much as the aluminum atom with respect to the nickel atom.
  • Example 10 The same operation as in Example 10 was performed except that the amount of styrene added was changed. As is clear from the results shown in Table 3, the molecular weight decreased with the amount of styrene added.
  • Example 10 The same operation as in Example 10 was carried out except that 4-mmol of 4-trimethoxysilylstyrene was added instead of styrene, to obtain 6.4 g (68%) of a norportene addition polymer.
  • the weight average molecular weight (Mw) was 162,000
  • the number average molecular weight (Mn) was 62,000
  • MwZMn was 2.6.
  • Example 14 The same operation as in Example 14 was carried out except that 8 mmol of 4-trimethoxysilylstyrene was added, to obtain 5.5 g (58%) of a norportene addition polymer.
  • the weight average molecular weight (Mw) was 103,000
  • the number average molecular weight (Mn) was 43,000
  • Mw / Mn was 2.4.
  • the content was 0.19 mol%, which was almost equal to that of one 4-trimethoxysilyl group bonded per molecule of the polymer. It was equivalent.
  • Example 10 The same operation as in Example 10 was carried out except that styrene was not added, to obtain 9.0 g (95%) of a norpolenene addition polymer.
  • the weight average molecular weight (M w) was 744,000
  • the number average molecular weight (Mn) was 243,000
  • Mw / Mn was 3.1.
  • the norpoleneene addition polymer obtained in Examples 10 to 15 and Comparative Examples 12 to 13 was cast from a cyclohexane solution, dried under vacuum at 200 ° C for 3 hours, and had a film thickness of 0. A 20 millimeter film was made.
  • the height of the absorbance peak at 700 cm- 1 was measured by free-transform infrared absorption spectroscopy, and the results shown in Table 3 were obtained for the polymers obtained in Examples 10 to 13.
  • the absorbance peak increased with the amount of styrene added.
  • the addition polymer of Comparative Example 12 in which styrene was not added no absorbance peak was observed.
  • the polymers of Examples 14 and 15 using 4-trimethoxysilylstyrene as a molecular weight regulator no clearly separated absorption was observed in the Fourier transform infrared absorption spectroscopy. .
  • a dry toluene solution of 2-norpolene (concentration: 4.8 mol Z liter) (16.8 ml) and 5-hexyl-2-norpolonene (4) were placed in a 200 ml reactor made of glass that had been thoroughly dried and purged with nitrogen. 1 milliliter and 50 milliliters of dry toluene were charged, and 0.1 milliliters (0.05 millimoles) of a 1,5-six-octane dry toluene solution (concentration: 0.5 milliliters) was added. Adjusted to 10.
  • Example 18 The same as in Example 18 except that the amount of added 1,5-cyclooctadiene was changed. The operation was performed. The norpolene content of each of the obtained cyclic olefin-based addition polymers was 80 mol%, and the molecular weight distribution was narrow as evident from the analysis results shown in Table 4, and the added 1,5-cyclooctane was added. The molecular weight decreased with the amount of the gen.
  • Example 18 The same operation as in Example 18 was performed, except that 1,5-cyclohexene was not added. From the results shown in Table 4, a cyclic olefin-based addition polymer having a broad molecular weight distribution was clearly obtained as compared with Examples 17 to 19. The polymerization activity was lower than those of Examples 17 to 18.
  • Example 17 The same operation as in Example 17 was performed, except that 0.2 mmol of 11-hexene was added instead of 1,5-cyclooctadiene. As is clear from the results shown in Table 4, a cyclic olefin-based addition polymer having a wider molecular weight distribution than Examples 17 to 19 was obtained. Further, the polymerization activity was equivalent to that of Comparative Example 14, and no effect of improving the activity was observed.
  • Example 20 The same operation as in Example 20 was carried out except that the amount of 1,5-cyclooctadiene added was 0.12 ml, to obtain 92.6 g (90%) of a cyclic olefin addition copolymer.
  • Example 21 The same operation as in Example 21 was performed except that 1,5-cyclooctadiene was not added, to obtain 87.3 g (85%) of a cyclic olefin-based addition polymer.
  • a cyclic olefin addition polymer of the present invention it is possible to obtain an addition polymer of a cyclic olefin having a polar group using a readily available catalyst component and without using a large amount of aluminoxane. Can be. Furthermore, a cyclic olefin-based addition polymer in which the molecular weight is controlled and an aromatic substituent is introduced at a molecular chain terminal can be obtained. Further, a cyclic olefin-based addition polymer having a controlled molecular weight, containing norpolene having a polar group as a structural unit, and further having an aromatic substituent at a molecular chain terminal can be obtained.
  • a cyclic olefin-based addition polymer having a controlled molecular weight and having a polar group-containing aromatic substituent at the molecular chain end can be obtained. Furthermore, an improvement in the polymerization activity of cyclic olefins can be obtained.
  • the cyclic olefin-based addition polymer produced by the method of the present invention has excellent heat resistance, optical properties, solvent resistance, chemical resistance, liquid crystal resistance, and homogeneity.
  • display device substrates various window materials, polarizing films, retardation films, liquid crystal films, optical films such as antireflection films, OHP films, substrates for printed circuit boards, etc., optical disks, optical fibers, lenses, prisms, Optical filter, light guide plate, optical waveguide Suitable for optical materials such as roads, electronic component materials such as semiconductor encapsulants, medical equipment, various containers, coating agents, adhesives, and binders.

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Abstract

L'invention concerne la polymérisation d'une cyclooléfine, comportant un groupe polaire spécifique, par polymérisation d'addition dans un solvant hydrocarboné à l'aide d'un catalyseur de polymérisation comprenant (i) un composé métallique de transition spécifique, (ii) un composé acide de Lewis, et (iii) un alkylaluminoxane, permettant d'obtenir un polymère d'addition de cyclooléfine. Dans une autre réalisation, on polymérise une cyclooléfine par polymérisation d'addition, dans le solvant hydrocarboné, à l'aide du catalyseur de polymérisation en présence d'un régulateur de poids moléculaire, comprenant au moins un composé vinyle aromatique, ou au moins un composé polyène cyclique non conjugué, ou les deux, afin d'obtenir un polymère d'addition de cyclooléfine.
PCT/JP2002/000453 2001-01-24 2002-01-23 Procedes de production de polymere d'addition de cycloolefine WO2002059168A1 (fr)

Priority Applications (3)

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US10/466,429 US6911507B2 (en) 2001-01-24 2001-01-23 Processes for producing cycloolefin addition polymer
DE60226310T DE60226310T2 (de) 2001-01-24 2002-01-23 Verfahren zur herstellung von cycloolefinadditionspolymerisat
EP02710329A EP1364975B1 (fr) 2001-01-24 2002-01-23 Procedes de production de polymere d'addition de cycloolefine

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JP2001015318A JP4894986B2 (ja) 2001-01-24 2001-01-24 ノルボルネン系環状オレフィン付加重合体の製造方法
JP2001-15318 2001-01-24
JP2001227249A JP4941621B2 (ja) 2001-07-27 2001-07-27 環状オレフィン付加重合体の製造方法
JP2001-227249 2001-07-27
JP2001-227248 2001-07-27
JP2001227248A JP5013033B2 (ja) 2001-07-27 2001-07-27 環状オレフィン付加重合体の製造方法

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EP1293521B1 (fr) * 2001-09-13 2008-02-13 JSR Corporation Copolymère d'addition d'une oléfine cyclique et procédé pour sa préparation, composition réticulable, produit réticulé et son procédé de préparation, et matériau optiquement transparent et son usage
CN1305922C (zh) * 2002-05-29 2007-03-21 Jsr株式会社 环状烯烃类加成共聚物以及光学透明材料
US7056999B1 (en) * 2002-10-08 2006-06-06 Jsr Corporation Cycloolefin copolymer formed by ring-opening polymerization, process for producing the same, and optical material
JP4075789B2 (ja) * 2003-12-05 2008-04-16 Ｊｓｒ株式会社 環状オレフィン系付加重合体の製造方法
JP5430066B2 (ja) * 2004-07-07 2014-02-26 プロメラス， エルエルシー 絶縁樹脂組成物及びその使用
JPWO2006067950A1 (ja) * 2004-12-22 2008-06-12 Jsr株式会社 環状オレフィン系付加共重合体の製造方法、環状オレフィン系付加共重合体およびその用途
WO2007034653A1 (fr) * 2005-09-22 2007-03-29 Zeon Corporation Polymère d'addition d'un composé du norbornène, procédé servant à produire celui-ci, article moulé comprenant le polymère et utilisation de celui-ci
KR20090034960A (ko) 2006-07-07 2009-04-08 제이에스알 가부시끼가이샤 환상 올레핀계 부가 공중합체, 그의 제조 방법 및 이 공중합체로부터 얻어지는 위상차 필름
JP2008031292A (ja) * 2006-07-28 2008-02-14 Fujifilm Corp ノルボルネン系重合体フィルム、ならびにそれを用いた位相差フィルム、偏光板および液晶表示装置
JP5389616B2 (ja) * 2009-11-18 2014-01-15 日東電工株式会社 赤外線反射基板
CN106661169B (zh) * 2014-09-10 2020-03-03 住友化学株式会社 共轭二烯聚合物和共轭二烯聚合物组合物

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WO1997033198A1 (fr) * 1996-03-07 1997-09-12 The B.F. Goodrich Company Compositions de photoresist comprenant des polymeres polycycliques avec des groupes pendants labiles acides
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US20040063873A1 (en) 2004-04-01
KR20020086676A (ko) 2002-11-18
EP1364975B1 (fr) 2008-04-30
US6911507B2 (en) 2005-06-28
TW593377B (en) 2004-06-21
DE60226310D1 (de) 2008-06-12

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